"Alpha"-Caryophyllene alcohol (Apollan-11-ol) is being used to investigate deuterium isotope effects as well as the mechanism of C-O epimerization in the photolysis of nitrite esters (Barton reaction). Methylated perhydroanthracenes with a functional group (OH) on the central ring will be prepared and the equilibrium for OH epimerization will be determined. The results should provide quantitative information on the effect of 2,6-diaxial substitution on the axial-equatorial partitioning of the functional group. Stereochemistry of carbene rearrangements will be studied with specifically deuterated caryolane and clovane derivatives. The substrates will be prepared by routes involving deuterioboration of olefins and lithium aluminum deuteride reduction of epoxides. Aza and thia analogs of polycyclic systems will be prepared. Kinetics of solvolysis of appropriate derivatives will be conducted to learn how heteroatoms can participate in ionization reactions. The chemistry and electron delocalization of related novel heterocyclics will be explored. The use of 13C nmr for location and assay of deuterium in complex molecules is being developed. Emphasis is on mechanistic studies of polyene cyclizations, hydrogen shifts and skeletal rearrangements.